Search

Solution equilibrium calculations were performed in this study to understand the impact of contaminant metal ions on the precipitation efficiency of selected rare earth elements (Ce3+, Nd3+, and Y3+) using oxalic acid as a precipitant. Trivalent metal ions, Al3+ and Fe3+, were found to considerably affect the precipitation efficiency of REEs. When Al3+ and Fe3+ concentrations were increased by 1 × 10−4 mol/L, in order to achieve an acceptable cerium recovery of 93% from solutions containing 1 × 10−4 mol/L Ce3+, oxalate dosage needed to increase by 1.2 × 10−4 and 1.68 × 10−4 mol/L, respectively. Such great impacts on the required oxalate dosage were also observed for Nd3+ and Y3+, which indicates that oxalic acid consumption and cost will be largely increased when the trivalent metal ions exist in REE-concentrated solutions. Effects of the divalent metal ions on the oxalate dosage is minimal. Furthermore, solution equilibrium calculation results showed that the precipitation of Fe3+ and Ca2+ (e.g., hematite and Ca(C2O4)∙H2O(s)) likely occurs during the oxalate precipitation of REEs at relatively high pH (e.g., pH 2.5), which will reduce rare earth oxalate product purity. In addition to the metal ions, anionic species, especially SO42−, were also found to negatively affect the precipitation recovery of REEs. For example, when 0.1 mol/L SO42− occurs in a solution containing 1 × 10−4 mol/L Ce3+ and 4 × 10−4 mol/L oxalate, the pH needed to be elevated from 2.0 to 3.3 to achieve the acceptable recovery. Overall, findings from this study provide guidance for the obtainment of high-purity rare earth products from solutions containing a considerable amount of contaminant metal ions by means of oxalic acid precipitation. Accepted version

Brassinosteroids (BRs) play essential roles in regulating plant growth and development, however, gaps still remain in our understanding of the BR signaling network. We previously cloned a grain length quantitative trait locus qGL3, encoding a rice (Oryza sativa L.) protein phosphatase with Kelch-like repeat domain (OsPPKL1), that negatively regulates grain length and BR signaling. To further explore the BR signaling network, we performed phosphoproteomic analysis to screen qGL3-regulated downstream components. We selected a 14-3-3 protein OsGF14b from the phosphoproteomic data for further analysis. qGL3 promoted the phosphorylation of OsGF14b and induced the interaction intensity between OsGF14b and OsBZR1. In addition, phosphorylation of OsGF14b played an important role in regulating nucleocytoplasmic shuttling of OsBZR1. The serine acids (Ser258Ser259) residues of OsGF14b play an essential role in BR-mediated responses and plant development. Genetic and molecular analyses indicated that OsGF14b functions as a negative regulator in BR signaling and represses the transcriptional activation activity of OsBZR1. Collectively, these results demonstrate that qGL3 induces the phosphorylation of OsGF14b, which modulates nucleocytoplasmic shuttling and transcriptional activation activity of OsBZR1, to eventually negatively regulate BR signaling and grain length in rice.

Due to the increasing criticality of rare earth elements (REEs), it has become essential to recover REEs from alternative resources. In this study, systematic REEs leaching tests were performed on the calcination product of a coal coarse refuse using hydrochloric acid and different types of organic acid as lixiviants. Experimental results show that the recovery of REEs, especially heavy REEs (HREEs) and scandium (Sc), is improved by using selected organic acids. Citric acid and dl -malic acid afford the best leaching performances; whereas, malonic acid, oxalic acid, and dl -tartaric acid are inferior to hydrochloric acid. Results of zeta potential measurements and solution chemical equilibrium calculations show that malonic acid is more likely adsorbed on the surface of the calcined material compared with citric acid and dl -malic acid. The adsorption may reduce the effective concentration of malonic species in solution and/or increase the amount of REEs adsorbed on the surface, thereby impairing the leaching recovery. Compared with light REEs (LREEs), a stronger adsorption of the HREEs on the surface is observed from electro-kinetic test results. This finding explains why organic acids impose a more positive impact on the leaching recovery of HREEs. By complexing with the HREEs, organic acids can keep the metal ions in solution and improve the leaching recovery. The adsorption of Sc3+ on the surface is the lowest compared with other REEs. Therefore, rather than complexing, the organic anionic species likely play a function of solubilizing Sc from the solid, which is similar to that of hydrogen ions.

It is critical to separate carbon from fly ash due to its increasing amount being produced per year and component requirements for secondary utilizations. Flotation is an efficient technique to fulfill this task. Effects of diesel emulsification using sodium petroleum sulfonate on unburned carbon flotation from a fly ash sample were studied. Flotation tests showed that carbon recovery was increased from 41% to 86% using the emulsified collector at the same dosage level (0.5 kg/ton) as diesel. Zeta potential measurements indicated that both the carbon and emulsified collector droplets carried negative charges within the studied pH range. For fly ash particles with high carbon content, adsorption bands of carbonyl bond (C O) were detected in the FTIR spectra, which agreed with the XPS characterization findings. XPS analysis indicated that the emulsified diesel (ED) collector interacted more intensively with the surface carbon-oxygen groups relative to the normal diesel collector. Finally, the improved efficiency of ED is proved to be related to its polar groups and reduced oil droplet size. The polar groups of ED (mainly sulfonate) interacted with the surface oxygen containing groups (e.g., C O and COOH) through hydrogen bonding and Lewis acid base interaction.

In this study, 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTCA) was introduced as a depressant for the flotation separation of apatite from calcite. The micro-flotation test results showed that good floatability of both apatite and calcite were obtained at around pH 8.5 when using sodium oleate (NaOl) as collector. Mixed minerals flotation test results showed that an efficient separation of apatite from calcite was achieved using PBTCA as depressant, which presented a selective depression for the calcite. Zeta potential measurements indicated that the addition of PBTCA prior to NaOl did not interfere the interaction between NaOl and apatite while it decreased NaOl adsorption on calcite surface.

The effect of depressant 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTCA) on the flotation separation of smithsonite from calcite was studied by micro-flotation and electro-kinetic tests. The micro-flotation results showed that good floatability of both smithsonite and calcite were achieved in the presence of sodium oleate. The depressant PBTCA selectively depressed calcite without interfering the floatability of smithsonite. The mixed minerals flotation results showed that efficiency separation of smithsonite from calcite was achieved using PBTCA as the depressant. Zeta potential measurements indicated that NaOl was able to adsorb on the PBTCA pre-treated smithsonite surface, but failed to adsorb on the PBTCA pre-treated calcite surface.

Effects of sodium chloride on the sulfidization flotation of cerussite (PbCO3) were investigated by micro-flotation tests, adsorption tests and zeta potential measurements. The micro-flotation test results indicated that sodium chloride effectively improved the sulfidization flotation performance of cerussite. The electrical double layers of cerussite particles were compressed in sodium chloride solution, thus providing more lead sites on the cerussite surface and promoting the adsorption of sulfide ions. In sodium chloride solution, more lead sulfide species were formed on the cerussite surfaces and improved its sulfidization flotation performance.

Selective depression of calcite in a monazite-calcite flotation system was systematically studied using micro-flotation and electrokinetic tests as well as X-ray photoelectron spectroscopy (XPS) characterization and solution chemistry calculations. Monazite was found to be depressed by both sodium silicate and sodium hexametaphosphate when calcium ions appeared in solution. It was hypothesized that co-adsorption of calcium species (CaHCO3+ and CaCO3(aq)) and Si ( OH ) 4 as well as SiO ( OH ) 3 - via hydrogen bonding formed a compact layer over the monazite surface, thereby reducing octanohydroxamic acid adsorption by steric hindrance. The use of citric acid or EDTA formed soluble chelates (e.g. CaCit− and CaEdta2−) with the calcium ions which negated the flotation suppression effect. An XPS study indicated that both EDTA and citric acid chemically adsorbed on the monazite surface, while the adsorption on the calcite surface was achieved mainly through hydrogen bonding. EDTA was more effective than citric acid due to two reasons: (i) citric acid itself presented stronger depression effects and (ii) citric acid has weaker chelating properties for calcium. Using 2.5 × 10−4 M octanohydroxamic acid, 0.05 g/L sodium silicate and 6 × 10−5 M EDTA, monazite recovery of more than 90% was achieved while recovering only 20% of the calcite.

Recovery of rare earth elements (REEs), especially heavy and critical REEs, from alternative resources such as coal refuse has recently become increasingly important. A natural leachate containing 6.14 ppm of REEs with a pH value of 2.70 was collected from a coal coarse refuse pile and utilized as a feedstock for REE recovery tests. The pH value of the natural leachate was gradually increased in a step-wise manner using a sodium hydroxide solution which produced several precipitates. A precipitate containing about 1.1% total REEs was obtained in the pH range of 4.85–6.11 while recovering >80% of the REEs contained in the original leachate. The leaching and staged precipitation process enriched both the critical and heavy REE fractions. The ratios of heavy-to-light (H/L) and critical-to-uncritical (C/UC) REEs in the precipitate were much higher than the coarse refuse material (H/L: 1.54 vs 0.21, C/UC: 1.51 vs 0.34). Additionally, the precipitate contained 18.4% Al, 1.7% Zn, 1.4% Cu, 1.1% Mn, 0.5% Ni and 0.2% Co. A solution chemistry study indicated that the hydroxide and hydroxysulphate precipitates of Al, Si and Cu produced in the pH range of 4.85–6.11 contributed to the fractionation of the REEs and other metal ions such as Zn, Mn and Co to the precipitate. The iron hydroxide precipitates formed at lower pH values did not contain a significant amount of REEs. An explanation may be the competitive adsorption between Al, which was present at higher solution concentrations, and REEs on the iron hydroxide and/or hydroxysulphate precipitate surfaces as proven by results of precipitation tests conducted on model solutions. A product containing 94% of a rare earth oxide mix was obtained by re-dissolution of the REE enriched precipitates followed by selective precipitation using oxalic acid. The overall results including an economic assessment indicate that leachate solutions generated naturally from coarse coal refuse may be a valuable source of critical and heavy REEs that can be effectively recovered and concentrated using staged precipitation.

Objective: To determine the underlying mechanism of miR-34b/c in regulating doxorubicin (Dox)-induced myocardial cell injury. Methods: The viability of mouse myocardial cells HL-1 was detected by MTT assay. The apoptosis of HL-1 cells was detected by TUNEL assay. mRNA expressions of ITCH, TNF-α and IL-6 were measured by qRT-PCR. Protein levels of ITCH, NF-κB, TNF-α and IL-6 were measured by western blot. Dual luciferase assay was performed to detect the regulation of miR-34b/c on ITCH. Mouse model of cardiomyopathy was induced by intraperitoneal injection of Dox. Results: Dox reduced HL-1 cell viability and activated NF-κB pathway in HL-1 cells. miR-34b/c expressions were gradually up-regulated and ITCH expression was gradually down-regulated in Dox-treated HL-1 cells. miR-34b/c expression had negative correlation with the mRNA expression of ITCH. Besides, ITCH was a target of miR-34b/c. miR-34b/c mimic reduced cell viability, suppressed ITCH expression, increased TNF-α and IL-6 level, and promoted NF-κB expression in nucleus and cytoplasm of HL-1 cells. Whereas silencing miR-34 protected HL-1 cells through regulating ITCH. Finally, we demonstrated miR-34 antagomir-protected myocardial cells in mouse model of cardiomyopathy. Conclusion: miR-34b/c decreased HL-1 cell viability and promoted the secretion of proinflammatory cytokines in Dox-induced myocardial cells through ITCH/NF-κB pathway.

The majority of rare earth elements (REEs) existing in the feed to coal preparation plants report to the coarse refuse streams which are transported for permanent storage in contained piles. In this study, an integrated flowsheet was developed based on laboratory test data which combines physical separation, pyrite bio-oxidization, heap leaching, selective precipitation and solvent extraction processes. The test data was obtained from (1) characterization of a number of natural leachate and solid samples collected from different preparation plants which process coals from a number of coal seams and (2) laboratory acid leaching and selective precipitation tests results. The highly-valued critical REEs (i.e., Y, Nd, Eu, Tb and Dy) were selectively leached from the refuse samples in the natural environment due to the acid generated by pyrite oxidization. The leachate samples were evaporated to remove water and obtain residual solids (i.e., dissolved solids in the leachates). The total REE content in the dissolved solids from a given leachate sample was 380 ppm, which was higher than the REE content of the coarse refuse material that generated the leachate (322 ppm). Acid leaching tests recovered as much as 80% of the total REEs from the coarse refuse samples using a 1.2 M sulfuric acid solution. Afterwards, the pH of the leachate was increased in a step-wise fashion which resulted in the production of precipitates containing 0.3–1.1% total REEs. A significant amount of contaminants, such as Fe, Al, and Ca, were eliminated in the sequential precipitation process, which allowed further upgrading using oxalic acid precipitation and/or solvent extraction. In the proposed flowsheet, the coarse refuse is arranged in heap leach pads and the acid needed for REE leaching is primarily produced from pyrite bio-oxidization, which enhances the selectivity of REE recovery and significantly reduces the cost. The successful application of the flowsheet would result in significant benefits to both the coal and rare earth industries.

The flotation separation of scheelite from calcite using sodium humate (SH) as a potential depressant has been studied through micro-flotation experiments, zeta potential and Fourier transform infrared (FT-IR) spectra measurements. The flotation results indicate SH exhibited selective depression effect on calcite in the presence of sodium oleate, achieving the flotation separation of scheelite from calcite. Zeta potential results indicate that SH strongly absorbed on calcite surface but negligibly on scheelite surface, which prevents the adsorption of sodium oleate on calcite surface. The FT-IR results also show that SH can be adsorb on the surface of calcite. Results shown a higher Ca density on the calcite than on scheelite surface, and that calcite can accommodate the interaction of SH.

In order to clarify the effect of copper contents on the corrosion resistance of stainless steel in biological environment, 316L-0Cu (wt%), 316L-1.5Cu (wt%), 316L-4.5Cu (wt%) and 316L-7.5Cu (wt%) coatings were prepared by laser melting deposition (LMD), and the microstructure and corrosion behavior in simulated body fluids (SBF) were studied. The results show that the planar growth, cellular crystal and dendritic microstructure are formed in the four kinds of LMD-produced coatings. With the increase of copper contents, the microstructure is refined, the corrosion resistance is decreased first and then is increased. This is because the copper oxide precipitates at the high-density grain boundaries, which can promote the passivation behavior. Under the combined action of Cr2O3 and Cu2O, the corrosion resistance of 316L-7.5Cu coating is closest to that of 316L-0Cu coating.

Phosphatic clay is a waste material produced during the beneficiation of phosphate ore, which likely poses severe environmental problems. In this study, a phosphatic clay containing 258 ppm of total rare earth elements (REEs) was used as a feedstock for REE recovery. By reacting with 0.1 M HCl at 75 °C for 3 h, around 36 % of light REEs and 65 % of heavy REEs were extracted from the raw material. However, after calcination pretreatment at 600 °C for 2 h, the recovery was increased to 73 % and 81 %, respectively, which are close to the recoveries obtained from the raw material using a much higher acid concentration of 1.2 M. Based on the findings from sequential chemical extraction tests and scanning electron microscopy analysis, the positive impact was explained by the decomposition and conversion of REE-bearing minerals into more leachable species. Using a higher calcination temperature of 900 °C, recovery of both the light and heavy REEs was largely reduced relative to the raw material. Mineralogical analyses showed that the dominant minerals existing in the material, such as muscovite, were fused and sintered during the calcination at 900 °C. These reactions likely caused the decreases in the recovery. The results and findings from this study will contribute to the beneficial uses of phosphatic clay and the production of REEs.

The dissolution of minerals provides elevated concentrations of alkaline earth metal ions such as calcium (Ca 2+ ) in water which may have a significant influence on flotation performance. The effects of Ca 2+ ions dissolved from calcite surfaces on the flotation performance of a monazite-calcite system have been investigated using micro-flotation tests followed by fundamental collector adsorption studies. The results indicate that specially adsorbed CaOH + via hydrogen bonding competed with hydroxamic acid for the phosphate-oxygen active sites on the monazite surface and decreased its hydrophobicity due to hydration. Electrostatically adsorbed CaOH + on monazite increased the adsorption density of hydroxamic acid through a chelating interaction. At higher dosages of calcium and hydroxamic acid, bulk and surface precipitation of calcium-hydroxamate occurs in the monazite-calcium-hydroxamic acid system.

Acid mine leachate (AML) may be a significant source of rare earth and other critical elements needed for the manufacturing of advanced electronics and renewable energy technologies. A systematic study was performed on a natural leachate collected from a coal preparation plant that treated bituminous coal containing elevated amounts of pyrite. The leachate contained 1.96 ppm total REEs, 2.52 ppm Zn, 2.15 ppm Ni, 1.22 ppm Cu, 0.77 ppm Co, and 25 ppm Mn. Sequential precipitation using simple pH control generated a pre-concentrate containing 0.82% total REEs, 1.08% Zn, 0.91% Ni, 0.50% Cu, 0.34% Co, 7.1% Mn. The pre-concentrate was further treated by re-dissolution using a 10 M HNO3 solution, which resulted in a solution pH of 1.5. The addition of oxalic acid to selectively precipitate the REEs followed by roasting of the precipitate generated a product containing >98% rare earth oxides. More than 95% of the Cu and Zn were recovered from the residual liquid using Na2S at pH 2 and 3, respectively. The CuS and ZnS contents in the corresponding concentrates were 60% and 58%, respectively. The majority of the Co and Ni remained in the residual liquid. Based on these findings, a process flowsheet was developed to recover the REEs and critical metals from AML.

Lithium recovery from the density fractions of Baker (namely West Kentucky No. 13) seam coal was investigated in this study. Proximate and elemental analyses showed that lithium contents in the 1.8–2.2 SG and 2.2 SG sink fractions were 185 ppm and 150 ppm, respectively, which are significantly higher than the average content of coal sources (12 ppm) and coal ashes (66 ppm) worldwide. Moreover, due to the high lithium contents and mass distribution, nearly 90% of the lithium present in the Baker coal sample was distributed in the two density fractions. Direct leaching using a HCl solution resulted in less than 10% lithium recovery, which was due to nearly 90% of the lithium being associated with insoluble solids as determined by the results from sequential extraction tests. Calcination of both density fractions under 600 °C for two hours followed by leaching resulted in recovery increases in the range of 70% to 80%. The pyro-metallurgical pretreatment step converted most of the associated lithium minerals to more easy-to-leach forms such as carbonate and metal oxide. Based on mineralogy characterization and leaching test results, it was concluded that the positive effects of calcination on lithium leachability resulted from the dehydration and disintegration of kaolinite as well as dehydroxylation and expansion of muscovite/illite. An analysis of the leaching kinetics revealed that the leaching rate of lithium was controlled by interface transfer and diffusion across the product layer and was negatively impacted when the calcination temperature exceeded 600 °C due to sintering of the kaolinite.

The modes of occurrence associated with rare earth elements (REEs) in bituminous coal sources were evaluated along with their potential recovery by calcination treatment at 600 ℃ followed by sequential extraction. The coal samples were collected from three different resources, i.e., Fire Clay, West Kentucky No. 13, and Illinois No. 6 seams. Sequential extraction tests indicated that the majority of REEs in the calcined samples occurred as metal oxides especially for the West Kentucky No. 13 calcined material (54% of total REEs), which is distinct from untreated coal and combustion byproducts from pulverized coal boilers reported in literature. In addition, heavy REEs were more likely associated with easily dissolvable forms (i.e., ion-exchangeable, carbonates, and metal oxides). The calcined samples were leached under weak acidic conditions with and without adding ammonium sulfate to recover REEs. About 13%, 24%, and 20% of the REEs were extracted from the Fire Clay, West Kentucky No. 13, and Illinois No. 6 materials, respectively, by leaching at pH 4.0. The addition of 1 M ammonium sulfate further increased the recovery values to 18%, 45%, and 32%, respectively. In addition, about 64% of HREEs were extracted from the West Kentucky No. 13 calcined material under this condition. As such, a significant portion of the REEs can be easily extracted from the samples obtained by calcining the coals at 600 ℃.

Rare earth elements (REEs) contained in coal and associated mineral matter exist in several forms including micro-dispersed minerals, ion adsorption onto clay surfaces, and chemically bound. Tests found that REEs can be effectively recovered from certain components of three coal sources by leaching under mild conditions followed by solvent extraction. A range of pH values were evaluated at solution temperatures of 25 and 75 ℃. When using 1.2 M of sulfuric acid, nearly 85% recovery of the REEs was extracted from the middlings material collected from an operating plant. Acid leaching of a second middling source from another plant resulted in 60% of the total REEs being recovered under the same leaching conditions. Solvent extraction treatment of the leachate produced from six different coal sources resulted in products containing up to 50% total REEs from feedstocks starting with around 300 ppm.

Flotation separation of scheelite from calcite is difficult due to the similarities in their surface properties. In this work, the flotation behavior of scheelite and calcite using oxidized paraffin soap(OPS), benzohydroxamic acid(BHA) and the mixed OPS/BHA collectors was investigated through micro-flotation experiments. The flotation results of single mineral experiments demonstrated a higher selectivity for the flotation of scheelite from calcite at pH 9 than individual OPS and BHA when using water glass as depressant. In order to probe the validity of the findings, mixed binary minerals experiments, contact angle and zeta potential experiments were also carried out successfully. Accepted version

Getting magnetite concentrate with extremely high Fe grade using reverse flotation method has become increasingly important due to the enhanced requirement of iron making industry. The coagulation in magnetite-concentrate flotation system may impose negative effect on flotation performance. This paper combined the DLVO calculation and microscope observation to study the coagulation behavior in the system. The result shows that the coagulation between fine magnetite and coarse silica particle is very likely to occur with energy barrier 1.5 × 10 −18 J at pH 10.0, which is much smaller than 1.6 × 10 −17 J and 3.3 × 10 −17 J for fine magnetite and fine magnetite-coarse magnetite particles. The coating of fine magnetite particle on silica surface was observed under microscope. Mechanical scrubbing increases the concentrate Fe grade and recovery by 1.5% and 8.5% respectively. Magnetite concentrate of 67.9% Fe grade and 71.5% Fe recovery was finally obtained.

The influence of conditioning on the flotation of pyrrhotite in the presence of chlorite was investigated through flotation tests, sedimentation tests, and X-ray photoelectron spectroscopy (XPS) analysis. The flotation results show that chlorite slimes dramatically impair the flotation of pyrrhotite. Sedimentation and flotation tests reveal that conditioning can effectively remove chlorite slimes from pyrrhotite surfaces, resulting in an enhanced flotation recovery of pyrrhotite. When mixed minerals were conditioned under the natural atmosphere, a faster conditioning speed and longer conditioning time decreased the flotation recovery of pyrrhotite. However, when mixed minerals were conditioned under a nitrogen atmosphere, a more intensive conditioning process provided better flotation results. XPS analyses illustrate that a faster conditioning speed and longer conditioning time under the natural atmosphere accelerates the oxidation of pyrrhotite, leading to a decrease in the flotation recovery of pyrrhotite. Published version

The activation mechanism of Pb(II) on the flotation of wolframite was systematically investigated. Micro-flotation test results showed that Pb(II) effectively improved the flotation of wolframite in the presence of benzyl hydroxamic acid (BHA). Maximum floatability of wolframite was achieved at approximately pH 8.5. Adsorption of the hydrolyzed species of Pb(II) occurred at this pH value, which provided more activated sites on the wolframite surface. As such, BHA-Pb complexes were formed on the wolframite surface, which increased the BHA adsorption. In addition, BHA-Pb complexes were also formed in solution, which replaced the Fe and interacted with the Mn on the wolframite surface. These findings were proved by the results of zeta-potential measurements, adsorption measurements, solution chemistry calculations, Fourier transform infrared spectroscopy (FTIR) analysis, and X-ray photoelectron spectroscopy (XPS) characterization. Accepted version

The effect of extraordinary degradation of phenol organics on the SnO 2 -Sb 2 O 3 /Ti electrode is investigated through experimental research and theoretical analysis. The phenol organics contained 4-chloro-phenol, 4-bromo-phenol, and 2-iodo-phenol. At a current density of 4 mA cm -2 and an electrolysis time of 12 h, the degradation efficiency of the phenols was over 98% with a relatively short degradation time, whereas the degradation time of the PbO 2 /Ti electrode surpassed 40 h while delivering 100% disposal efficiency. Therefore, the effectiveness of electrochemical (EC) oxidation by the SnO 2 -Sb 2 O 3 /Ti was superior to that of the PbO 2 /Ti electrode. At the same time, the SnO 2 -Sb 2 O 3 /Ti had higher oxygen generation potential and lower electron consumption than the other electrodes. This was mainly due to the effect of the middle Sb 2 O 3 layer, which due to its high porosity and good catalytic effect, contributed to a better catalysis than the SnO 2 part.